Polyetherketonimides

Abstract

Polyetherketoneimides and copolymers thereof having an imide repeat unit of formula <IMAGE> wherein Ri is <IMAGE> in which A is a direct bond or -O-or another substantially non-electron-withdrawing group, and/or Ra is an at least partly arylene moiety other than m- or P-phonylene. These polymers tend to have improved melt stability and other properties, especially when made from a pre-existing imide monomer, instead of by the known amic acid route which results in uncyclised amic acid residues in the polymer.

We claim: 
     
       1. An ether-ketone-imide polymer comprising an imide repeat unit derived from a pre-existing imide monomer, which imide repeat unit has the formula ##STR48## wherein R a  is a substituted or unsubstituted at least partly arylene moiety attached by arylene ring carbon atoms to the adjacent --CO-- groups of the imide repeat unit; each Ar independently is a substituted or unsubstituted arylene moiety; and each n independently is 1 or 2;   which ether-ketone-imide polymer is substantially free of unimidized amic acid moieties.   
     
     
       2. A polymer according to claim 1, wherein each Ar is independently substituted or unsubstituted p-phenylene; m-phenylene; 3,3'-, 3,4'-, or 4,4'-biphenylene; or 2,6-naphthylene. 
     
     
       3. A polymer according to claim 1, wherein R a  is ##STR49## 
     
     
       4. A polymer according to claim 1, wherein R a  is m- or p-phenylene. 
     
     
       5. A polymer according to claim 1, wherein R a  is p-phenylene. 
     
     
       6. A polymer according to claim 1, wherein all of the Ar moieties are phenylene. 
     
     
       7. A polymer according to claim 1, wherein the imide repeat unit is ##STR50## 
     
     
       8. A polymer according to claim 1, wherein the imide repeat unit is ##STR51## 
     
     
       9. A polymer according to claim 1, wherein the imide repeat unit is ##STR52## 
     
     
       10. A polymer according to claim 1, wherein the imide repeat unit is ##STR53## 
     
     
       11. A polymer according to claim 1, which is partially crystalline. 
     
     
       12. A polymer according to claim 11, which has at least 20 percent crystallinity as measured by X-ray diffraction. 
     
     
       13. A polymer according to claim 1, wheein substantially all of the imide repeat units incorporate the unchanged cyclic imide form of the imide monomer. 
     
     
       14. An ether-ketone-imide copolymer comprising (I) an imide repeat unit as defined in any one of claims 1, to 10, and (II) a further repeat unit, which copolymer is substantially free of unimidized amic acid moieties. 
     
     
       15. An ether-ketone-imide copolymer comprising (I) an imdie repeat unit as defined in claim 1 and (II) a further repeat unit which is an arylene ether ketone repeat unit. 
     
     
       16. A copolymer according to claim 15, wherein the arylene ether ketone repeat unit is selected from the group consisting of: ##STR54## 
     
     
       17. A copolymer according to claim 16, wherein the imide repeat unit is ##STR55## and the further repeat unit is of formula (V) or of the isomeric form of formula (XI) corresponding to the isomeric form of the imide repeat unit. 
     
     
       18. A copolymer according to claim 16, wherein the imide repeat unit is ##STR56## and the further repeat unit is of the isomeric form of formula (VII) corresponding to the isomeric form of the imide repeat unit. 
     
     
       19. A copolymer according to claim 16, wherein the imide repeat unit is ##STR57## and the further repeat unit is of formula ##STR58## 
     
     
       20. A copolymer according to claim 16, wherein the imide repeat unit is ##STR59## and the further repeat unit is the p-form of formula (VII). 
     
     
       21. A copolymer according to claim 15, which is partially crystalline. 
     
     
       22. A copolymer according to claim 15, which has at least 20 percent crystallinity as measured by X-ray diffraction. 
     
     
       23. A copolymer according to claim 15, comprising less than 50 mol percent of the imide repeat unit. 
     
     
       24. A method of manufacturing a polymer or copolymer according to claim 11 or 15, comprising polymerizing (a) an imide monomer corresponding to the part of said imide repeat unit containing the N atoms and having terminal Ar moieties, which terminal Ar moieties have either (Case 1) at least one reactive hydrogen and no acyl groups on each terminal Ar or (Case 2) at least one reactive hydrogen on one terminal Ar and acyl halide group on the other terminal Ar with (b) an aromatic diacyl halide in Case 1 or with itself in Case 2 in the presence of a Lewis acid catalyst. 
     
     
       25. A method according to claim 24, wherein a Lewis base controlling agent for the Lewis acid catalyst is included in the polymerization reaction mixture.